Alkylation process



Oct. 15, 1946. C, R, RINGHAM 2,409,389

ALKYLATION PRocEssy Filed Sept. 28, 1944 Patented Oct. 15, 1946 UNITED V STATES PATENT OFFICE ,N

Clarence R. Bingham, Oklahoma. City1 Okla., `asksignor to Phillips Petroleum Company, a corporation of Delaware npplicationseptember 28, 1944', .Se'rlalNa 556,208 s claims. (o1. ctc-csail normal paralins, ,cycloparaiins and aromatic hydrocarbons. In such processes these catalysts have been used as such, suspended inor dissolved in a reaction mixture, suspended on solid supports such asactive carbon, Activated Alumina or aluminousmaterials such as bauxite, active silica, and various clays such as fullers earth, kieselguhr, etc., and 4as separate liquids in the form oi' complexes with organic and inorganic compound-s, The more usefulof the liquid complexes are those formed With `parailln'ic hydrocarbons, lespecially those formed with more or lesshighly lbranched normallyv liquid paramn hydrocarbons boiling in the `boiling ranges of those fractionsgenerally identi-ned asgasoline and kerosene. In many in-v stances i-t is desirable to have present a small amount of :a hydrogen halideJ sometimes `cnly about 0.1 to about l to 5 perrcent by Weight. This material may be present as aresult of side=re actions, such as when water is present in a charge stock, when an organic halogen compound is present in a charge stock, when some interreactionvbetiveen the aluminum halide and hydrocarbon takes place, or when a hydrogen halide isy deliberately added. ySince itisysubstantially limpossible to effect complete. dehydration ofVV all equipment andmaterials, especially in acommercial process, conversions with aluminumhalide catalysts` are often conducted without` the knowledge or appreciation that'minor amountsof a hydrogen halidearepresent. f

As alkylating reactants vfor use in alhylation processes -for reaction with-alkylatable hydrocarbons low-boilingole-ns are generally used` VHowever, other alliiylating` reactants have` also been proposedsuch as alkyl halides and alcohols. Otten the products of the alkylation Will not -result from structural addition'of the alkylatingreactant to the alkylatable Ahydrocarbon. Thus,

when -isobutane is. reacted with ethylene. in then presence of aluminum halidecatalysts one of the mdljor` products -is diisopropyl, although structurally this product is not ethyl isobutane even though it is a hexane. However, in many instances structural addition products are obtained, as. when ethylene reacts with benzene to form l ethylbenzene or when isopropyl alcohol or an isopropyl` halide reacts with benzene to form isoprop ylbenzene.

The commercial practice of suchY alkylation processes presents `numerous problems which are not ,found in laboratory operation and which often cannot be foreseen. on the basis of results obtained in laboratory runs.` Y One of the :greatest diuculties experienced in commercial operations is the efficient use of equipment while securing, atthe same time, uniform operation over an extended period of time. It is particularly important to have uniform catalyst activity during an extended period of operation, such as one lasting for several Weeks, in order that uniform volumesiof materials may be treated and uniform reaction efliuents may be available for treatment in separating equipment having a fixed size and operated `at maximum eiiiciency. I `have found that an aluminum halide-hydrocarbon complex maybe used as a catalyst in commercial operationsfor the alkylation of hydrocarbons and satisiactorzily uniform catalyst activity may be established and maintained, and at the same time a number of. relatively small reactors may be used to treat large quantities o f material, by the speciiic method of combining groups of reactors and catalyst settlers, and by combining all of the used catalyst before itis returned back to the individual reactors, in a Vmanner which will be more `fully and completely disclosed in connection with the accompanying drawing. Y

An object .ofthis invention is to convert hydrocarbons in the presence of a `hydrocarbon-alu minum halide complex catalyst.

Another object of this invention is to effect an Valkylation reaction between an alkylatable hydrocarbon andanvalkylating reactant in a ,continuous commercial process.

Still another. object Ofthis invention is to btain. uniform reaction. in an alkylation process Whileat the same time using a large number of relativelyfsmall reactors'.

Still another object of this invention is to react isobutane and ethylene to produce high yields of diisopropyl. n

Otherobjects and advantages .of this invention will become apparent, to `one skilled in the art, from the accompanying disclosure and discussion.

A preferred embodiment of my invention will now be discussed in some detail in connection with the accompanying drawing which forms a part of this application, and which shows an arrangement of apparatus suitable for practicing the invention. While various features of the invention will be discussed in connection with the reaction of isobutane and ethylene to produce diisopropyl in the presence of a liquid aluminum chloridehydrocarbon complex as the catalyst, it is to be understood that the invention can be applied tov other reactants and to other liquid catalysts.

Referring now to the drawing, an isobutane stream is passed to the process through pipe I and a mixture of isobutane and ethylene is passed to the process through pipe I I. AS will be appreciated by those skilled in the art in-a commercial plant these hydrocarbons will be accompanied and with a hydrocarbon to catalyst ratio within the reactor of 3:2 and a flow rate of 1.25 gallons of alkylate per gallon of catalyst per hour, the ow rate of alkylate should be such that 500 gallons of alkylate are produced per hour.

The catalyst itself is substantially insoluble in hydrocarbons and hydrocarbons are not substantially soluble in it. It is preferred to have a volume ratio of hydrocarbons to catalyst in the reaction zone between about 9:1 and about 1:1 and the preferred ratio has been found to be about 3:2. When the reaction mixture is maintained intimately admixed with the catalyst under the preferred conditions the hydrocarbon phaseis the continuous phase. Under these conditions the catalyst readily separates from the a hydrocarbons and power requirements in order by comparatively small amounts of other hydrocarbons. Such hydrocarbons, however, should be present in relatively small amounts, particularly when they are also reactive under the reaction conditions. One rather typical composition for c ach of these streams will be presented in the specific example given hereinafter. The alkylation reaction is conducted in four reactors-I2, I3,`I4, and i5-with reactors I2 and I3 being operated in series and reactors I4 and I5 being operated in series, the first said set of reactors being operated in parallel to the second set of reactors. More than two such sets of reactors may, of course, be used if desired. Contents of each reactor are intimately admixed by means of a stirrer 20. The isobutane stream is passed through pipes i6 and I'l in two portions to the bottom of each of reactors I2 and I4, which are the primary reactors in each set. A catalyst stream from a common catalyst source, such as pipe 2l, is passed in two portions through pipes 22 and 23 to the bottoms of reactors I2 and I4. This catalyst stream comprises used and fresh catalyst as will be more thoroughly discussed hereinafter. The isobutane-ethylene stream is split into six portions. To the bottom of each of the primary reactors I2 and I4 is added one of these portions through pipes 24 and 25. To the middle of each of the two primary reactors I2 and I4 is added another portion through pipe 26 and 2. A recycled portion of the hydrocarbon effluents of the reaction is passed throughA pipe and divided into two portions which are passed through pipes 3| and 32, each portion also being added to the bottom of the primary reactors I2 and I4.

" A preferred reaction temperature for this conversion is between about 50 and about 200 F., preferably about 80 to about 150 F. When alkylating hydrocarbons the activity of the catalyst herein described is sufficiently high that even ethylene undergoes rapid reaction within this temperature range. Itis generally preferred to operate under a pressure such that the hydrocarbons are present in the reaction Zone substantially in liquid phase and in many instances the hydrocarbon material will be kept in completely liquid phase under the preferred reaction conditions. The flow rate of reactants to the reaction zone is preferably expressed in terms of amount of product produced, and when reacting isobutane with ethylene to produce diisopropyl I prefer to operate at flow rates between about 0.2 and about 1.5 gallons of total alkylate produced per gallon of catalyst present in the reactor per hour. Thus, when reacting isobutane and ethylene in a reactor having 'a total internal volume of 1,000 gallons to maintain a suitable intimate admixture are not excessive. However, when a greater amount of catalyst is used, it has been found that a phase inversion may take place with the result that the catalyst phase is the continuous phase and the hydrocarbon phase the discontinuous phase, which is not nearly so satisfactory. Under such conditions it is quite difficult to obtain adequate physical separation between the hydrocarbon phase and the catalyst phase and a considerable amount of power is required in order to adequately mix hydrocarbons and catalyst charged to the reaction zone.

As the mixture of reactants and catalyst passes up through the primary reactors it is thoroughly admixed so that the catalyst is present in extremely small particles. From the top of each of the primary reactors this intimate admixture is passed, through pipes v33 and 34, to the bottom of the corresponding secondary reactor. At this point the final two portions of the isobutaneethylene mixture arev added, through pipes 35 and 36. rThe hydrocarbon-catalyst mixture is also intimately admixed in the secondary reactors I3'and I5 to effect suitable reaction. The resulting admixtures are passed through pipes 31 and 38 to corresponding primary settlers 40 and 4I. These settlers are preferably vessels set on a slope with a solid bafiie plate 42 and 43 near the inlet and extending about halfway up in the tank. This baffle plate serves to distribute the incoming emulsion across the tank section, thereby tending to reduce the short-circuiting eiect,` and also serves as a retainer wall for the catalyst which settles out. The liquid catalyst which settles out is removed through pipes 44 and 45 and combined to form a common catalyst source in pipe 2|. A pipe 39 is provided joining efliuent pipes 31 and 38 for use in case of emergency if one of the set` tling tanks 40 or 4I needs to be taken out of service. Ordinarily this` pipe 39 will not be used.

From the top part yof settling tanks 40 and 4I a hydrocarbon mixture is passed through pipes 46 and 4i and is combined in pipe 50. A substantial portion of this combined hydrocarbon material is passed through pipe 5I to cooler 52 and is returned to the reactors through pipe 30 as previously discussed. Since this combined hydrocarbon material still contains a small amount of entrained catalyst, generally, however, not more than about two or'three to about eight or ten per cent of the total catalyst, the remaining portion is passed to a secondary settler 53. Since the catalyst which is still present in the hydrocarbon material is quitenely divided and represents the finely divided particles present in the emulsion passed from the secondary vreactors through pipes 31 land 38, a somewhat longer seti tling time is necessary in settler 5.3 than wasused in either settlers door 4|. Catalyst `whichrsepa=- rates out ispassed through pipe `5t for admix` ture with the catalyst removed through pipes l44 and l5. ,i i p A liquid hydrocarbon material substantially free from catalyst and containing unreacted hydrocarbons andalkylate is passed` from settler 53 thro-ugh pipe 55 toseparating means 60. Generally it will ber desirable to wash this hydrocarbon material with an' alkaline solution, to remove any Vacidic materials which may be present, before the material is subjected to fractional distillation. A diisopropyl fraction is Aseparated and removed through pipe `62 las a product ofthe process. Unreacted isobutane is separated and returned tothe process through pipe 63.- 'Normal butano, which will include that initially accom* panying thechar-ge stockand any normal butane formed byisomerization :during `the alkylation process, `may be separated and discharged through pipe 64. One or more other alkylate fraction may also be recovered, as through pipe 65. `Any undesired light gases may be discharged through pipe. i v

Aluminum chloride is the halide which will most generally be used in ythe practice of my invention althoughit is Anot outside of the broadest concepts of my invention to i use other aluminum hal-ides, particularly aluminum bromide. While aluminum fluoride generallydoes not givesatisfactory results, vmixed halides such as AlClzF, AlClFz, AlBraF, and the like, `may-often be usedv successfully Liquid hydrocarbonsaluminum halide catalysts are. generally prepared by reacting a relatively pure and substantially anhydrous aluminum halidewiith `a paranin hydrocarbon, or paraflinic hydrocarbon fraction, at -al temperature between about 1510 and about 230 F. Usually, butnot always, it isidesirable to .eflrect thelproduction of the Acatalystbytadding duringits tori-nation Aa small amount of a hydrogen halide and to lmiX' vigorously the hydrocarbon `and 4alur-n-inurn halide until the resulting .complex contains .in combination from about 5G to about T0 per cent by weight of aluminum halide. fSatisfactory fluid complexes have-been prepared from fav-ariety of paraffin hydrocarbons'including normal heptane, isooctane, a parainic .alkylate l`.fraction resulting from reaction of isobutane and butylenes, and boiling `above 350 F., an oleflnic polymer fraction 'boiiingi-nV the upper part :of the gasoline range, and kerosine. nnr essential re fquirement for the preparationof agood catalyst appears to be the use of a-suiiiciently powerful mixing to maintain the aluminum halide and the hydrocarbon intimate contact during the period the Vcatalyst is being prepared. In the ini'. tial stage individual particles of aluminum halide appear to become -coated with a layer of sticky complex and ifthe mixing power is not great `enough such particles tend to accumulate vand/'or agglomerate'to form a viscousmass which settles to the bottom of thereaction vessel and-further formation of the desired complex is inhibited or prevented, `since unreacted aluminu-mhalide no longerhas access tothe hydrocarbon phase. Two general types of catalyst have been prepared. These 'may be -characterized as high-aluminum halide and low-aluminum halide types. `When preparing a catalyst with aluminum `chloride the high-aluminum chloride type contains 80 vto 85 'per cent by weight of aluminum chloride vand is *a* -yellow highly viscous material'. Thel lowaluminum chloridetype` contains about -55- per cent .byweight-of `aluminum chloride, isa fluid red-brown oil' having `a viscosity less `than `200 c'entistokes at 100 F., and is used as theactual catalyst. v'Thehigh-aluminum chloride typecan be `added during a continuous run in :small amounts tol-the recirculated catalystinorder to maintain Acatalyst activity. i Catalyst s activity, however,` can be maintained in other ways, as: by adding aluminum halide directly to `recirculated catalyst or by dissolving aluminum halidein one of the streams charged to the reaction zone. The liquid complex should not lie-contaminated with water or other reactive, oxygen-containingk compounds.

Inmaking the original batch of catalyst 'kerosene or other hydrocarbon may be added-through pipe 10 to a catalyst preparation vessel Hand an aluminum halide such as aluminum` chloride may be added through pipe 12. These materials may be intimately admixed by means of a stirring mechanism 13. After the process has been `started the activity of the recirculated catalyst `may be 'maintained by passing a portion of the recirculated catalyst through pipe 'M to Vessel ll wherein aluminum chloride, 'either as such vOras-a high-aluminum chloride complex `such as previously discussed, may be intimately mixed 'with it. The resulting fortified catalyst is passed through pipe 'l5 Vandireturned to pipe 2|`wherein it is mixed with the recirculatedcatalyst. `Since such `treatment tends to increase the total volurne` of catalyst available it will generally be found necessary to maintain 'a desired'volume of catalyst by withdrawal of material from pipe `through pipe 16. 'When it 'is desired to usel a hydrogen halide in preparing the catalyst suchmaterial may be added through either of pipes 10 or 112. In such instances it is often not necessary to add` hydrogen halide to the reaction system. However, if it is found desirable at. any time to add a hydrogen vhalide to the reaction system, any desired portion may' be added through pipe 1T! lto the catalyst present in pipe 2 i. By maintaining total emulsincation in all of the reactors in such a catalytic alkylation procrecycle system, and this will establish definitely y the condition of the catalyst in all parts of the system. ySuch an arrangement is markedlyrdifgferent'from a system wherein each reactor and its settler are separate from the other .reactors and settlersfor in which a settlerisi-madeintegral with each reactor proper with allowance "being made for return of the catalyst directly Iromthe settler to the reactor. When any vsample `taken from the system shows theV catalyst to be below the desired activity level, a predetermined quantity of the catalyst phase will be withdrawn from the catalyst recycle line, and an equivalent amount of fortilied catalyst addedat that point. Catalyst withdrawal and addition may be either a batch or a continuous process.

It Will be appreciated that the drawing vist a schematic representation oi process flow, and of equipment-whichmay be used in lconducting `my invention upon a commercial basis. Various specic pieces of equipment such as alkylation contactors, fractional distillation columns, pumps, control valves, heaters, coolers, 'catalyst chambers, and the like are well known to those skilled in the art and suitable equipment can be `readily assembled for any specific application of` my invention, by one so skilled, by following the teachings contained herein. e

As an example of the operation of my invention, an isobutane feed stock is charged to the apparatus illustrated in the drawing through pipe Ill. This stream has the composition shown in the accompanying table and is-charged in a continuous stream in the amount indicated. An isobutane-ethylene mixture is prepared by-using a liquid isobutane stream, from the same source as the isobutane feed, as an absorption liquid in a demethanizer to which is charged, as a gas, an eiliuent stream from a process for converting an ethane-propane mixture to ethylene. This iso- Abutane-ethylene mixture has the composition shown in the table and is charged in the amount shown. The isobutane is split into two equal portions and the isobutane-ethylene stream is split into six equal portions. To the bottom of each of reactors I2 and,I4 is passed one of the isobutane portions, one of the isobutane-ethylene portions, one-half of the recycle passing through pipe 3U, and about 6,150 volumes per day of a liquid hydrocarbon-aluminum chloride complex catalyst from pipe 2I. To the middle of each of the primary reactors I2 and I4 is charged another one of the six portions of the isobutaneethylene portions. As the hydrocarbon-catalyst mixture passes upwardly through these reactors Isobutane Isobutane- Net Recycle feed pipe ethylene eiliuent pipe l feed pipe ll pipe 55 51 Volume/day 6, 363 3, 318 9, 156 140, 000 Comp., mol percent:

M e t h a n e a n d lighter 10. 4 4. 5 Ethylene. 35. 3 1. 2 Ethane 13.2 5. 7 Propylene. 3. l 0.0 Propane.... 2. 9 5. 3 Isobutane 32.4 61.5 N. butane 2.7 8.0 Diisopropyl 8. 6 Other 5. 2

it is intimately admixed by the efficient stirrer 2t. lThe proportions of the materials charged insure that the liquid hydrocarbon mixture is'in the continuous phase, with finely divided particles of the liquid catalyst complex, having a maximum particle diameter between about l0 and 20 microns, dispersed throughout. The reaction temperatureranges up to about 125.F.a's a maximum, and the volume of cooled recycle is such 4vthat the overall temperature rise is not more than about to 20 F. Under these conditions liquid phase operation isassured with a pressure not, greater than about 40G-420 pounds per square inch gage. From the top of each ofthe primary reactors, the reacting admixture passes to the bottom of the Acorresponding secondary reactors, I3 and I5, with one of the remaining two portions of the isobutane-ethylene charge being added just as it enters the secondary re'- actor. Each of the primary and secondaryreactors has a capacity of about '72 volumes. The upowing material is also intimately admixed in the secondary reactors, and Vpasses from the top of each secondary reactor to a corresponding sit CPI

primary settling zone, having a sufficient size to provide a settling time vof about 5 minutes, which is sufficient to permit removal of about per cent of the dispersed catalyst. The resulting hydrocarbon mixtures are combined, and a lmajor portion is cooled and recycled, in thevamount shown in the table. The remaining portion of thev combined mixtures passess to a secondary setling zone, which has a suicient size to provide a settling time of about 30 minutes. The catalyst which settles out from each of the three settling zones is combined, a portion (about 14 volumes per day) is discharged from the system through pipe 16, another portion is passed to a catalyst make-up vessel 7l, where it is fortified by the addition of fresh solid aluminum chloride. The resulting fortified catalyst is blended with the major part of the catalyst in pipe 2I to form a source of catalyst supply, with a uniform catalyst of high activity for the whole system. The hydrocarbon eiiiuent from the secondary settler, in an amount shown in the table, is washed with aqueous sodium hydroxide and passed to separating means 6E) for separation and recovery of various fractions. This net hydrocarbon effluent has the composition shown in the table. Except for a small amount of entrained catalyst, the hydrocarbon recycle passing through pipes 5I and 30 has the same composition.

It is to be appreciated that various modifications of my invention can be practiced without departing from the teachings and spirit of the disclosure, or from the scope of the claims. The claims are not to be unduly limited by limitations shown in the specific examples.

I claim:

1. An improved process for reacting ethylene and isobutane to form diisopropyl, which .com-

prises conducting said reaction in two sets of reactors having two reactors in each set, passing a portion of an isobutane feed to the bottom of the first reactor of each set, passing a portion of an isobutane-ethylene feed to the bottom of each of said reactors and also to an intermediate point of the first reactor of each set, passing from a common catalyst source a portion of a liquid aluminum chloride-hydrocarbon complex catalyst to the bottom of the first reactor of each set in an amount not greater than that which will permit said catalyst to be the dispersed phase in the resulting admixture, maintaining an alkylation temperature in each said reactor, passing an intimate hydrocarbon-catalyst admixture from the top of the first reactor of each set to the bottom of the second reactor of the respective set, flow,- ing the contents of each reactor from bottom to top and effecting a vigorous stirring of the contents of each said reactor to establish an intimate admixing of the contents thereof, passing the eiiluents of each second reactor to a corresponding primary settling zone to separate a liquid hydrocarbon material containing a minor amount of entrained catalyst from the bulk of the admixed catalyst, combiningthe hydrocarbon eliluents of each primary settling zone and combining the catalyst effluents of each primary settling zone, passing at least a portion of said combined hydrocarbon eiiluents to a secondary settling zone wherein substantially all of the remaining entrained catalyst is separated fromthe effluents, removing from said secondary settling zone a hydrocarbon materialand recovering therefrom a diisopropyl fraction as a product of the process, removing also from said secondary settling zone liquid catalyst, and combining said liquid catalyst with the aforesaid combined catalyst eliiuents to form a uniform catalytic material as the aforesaid common catalyst source.

2. In a process for reacting an alkylating reactant and an alkylatable hydrocarbon in tbe presence of a liquid alkylation catalyst under alkylation reaction conditions, the improvement which comprises conducting said reaction in at least two series of reactors having two reactors in each set, passing an alkylatable hydrocarbon feed to the bottom of the first reactor of each set, passing a mixture of alkylatable hydrocarbon and alkylating reactant to the bottom of each of said reactors and also to an intermediate point of the rst reactor of each set, passing from a common catalyst source a portion of a liquid allrylationrcatalyst to the bottom of the iirst reactor of each set in an amount not greater than that which will permit said catalyst to be the dispersed phase in the resulting admixture, passing an intimate hydrocarbon-catalyst admixture from the top of the iirst reactor of each set to the bottom of the second reactor of the same set, owing the contents of each reactor from bottom to top and effecting a vigorous and'intimate mixing of the contents of each said reactor, passing the eiiluents of each second reactor to a corresponding primary settling zone to separate a liquid hydrocarbon material containing a minor amount of entrained catalyst from the bulk cf the admixed liquid catalyst, combining the hydrocarbon eiiiuents of each primary settling Izone and combining the catalyst efliuents of each primary settling zone, cooling a portion of said combined hydrocarbon eiliuents and passing saine to the bottom of the iirst reactor of each said set, passing a further portion of said combined hydrocarbon eiiluents to a secondary settling zone and removing therein substantially all of said entrained catalyst from the hydrocarbon efliuents, recovering an alkylate product from the resulting hydrocarbon eiiuents, admixing said separated catalyst with the aforesaid combined catalyst effluents to produce a common catalyst source as aforesaid, and adjusting the catalyst contained in said common catalyst source to maintain a desired catalytic activity by withdrawal of a portion thereof as spent catalyst and by addition of fresh catalytic constituents.

3. The process of claim 2 in Which said alkylatable hydrocarbon is a low-boiling isoparaiiin, said alkylating reactant is a low-boiling olen, and said liquid catalyst is a liquid hydrocarbonaluminum chloride complex.

CLARENCE R. RINGHAM. 

